Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/0014—Use of organic additives
  • C08J9/0023—Use of organic additives containing oxygen
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C33/00—Moulds or cores; Details thereof or accessories therefor
  • B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
  • B29C33/60—Releasing, lubricating or separating agents
  • B29C33/62—Releasing, lubricating or separating agents based on polymers or oligomers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
  • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
  • C08G18/6629—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/101—Esters; Ether-esters of monocarboxylic acids
  • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2110/00—Foam properties
  • C08G2110/0008—Foam properties flexible
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2110/00—Foam properties
  • C08G2110/0033—Foam properties having integral skins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2110/00—Foam properties
  • C08G2110/0041—Foam properties having specified density
  • C08G2110/0066—≥ 150kg/m3
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2120/00—Compositions for reaction injection moulding processes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2125/00—Compositions for processes using internal mould release agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2410/00—Soles
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
  • C08J2375/04—Polyurethanes

Definitions

• the invention relates to a new process for the production of optionally microcellular, elastomeric polyurethane moldings with a closed surface layer having an average density of 0.8 to 1.4 g / cm 3 , certain condensation products of ricinoleic acid being used as internal mold release agents.
• release agents described in these prior publications are particularly well suited for the production of rigid molded polyurethane-based foams with a closed outer skin, i.e. they give these moldings good to very good self-separating properties.
• Shaped bodies of this type are generally produced by reaction injection molding using reaction mixtures containing highly active catalysts from organic polyisocyanates, higher molecular weight polyhydroxyl compounds and chain extenders (see, for example, DE-AS 2 622 951).
• the manufacture of such special, elastomeric molded articles still poses the unsolved problem of how the molded articles could be given satisfactory self-separating properties.
• DE-OS 2 121 670 describes certain binary or ternary mixtures as release agents in the production of preferably hard molded foams, the release agent component in said mixtures including hydroxyl-containing esters of monocarboxylic acids can also be used.
• Long-chain fatty and oleic acids on the one hand, and various alcohols, among other things, include simple alkane diols, such as ethylene glycol or hexanediol, as structural components for these esters.
• the long list of suitable fatty or oleic acids also contains ricinoleic acid.
• DE-OS 2 404 310 recommends the use of reaction products of ricinoleic acid with long-chain fatty acids, including free carboxyl groups, of polyricinoleic acids, which have free carboxyl groups and can be obtained by self-condensation of ricinoleic acid, as internal release agents in the production of various types of molded foams.
• carboxyl groups are only of limited suitability for highly active systems as processed by the reaction injection molding technique and used for the production of high-density elastomeric moldings, since they interfere with the sensitive catalysis of these systems.
• the release agents of this prior publication can also be used to produce molded high-density molded foams with good self-releasing properties
• the disadvantage of the release agents is that the mold inner walls have to be cleaned at short intervals in the series production of such molded articles, otherwise the self-releasing properties disappear after a few reaction cycles.
• Starting materials a) for the process according to the invention are any organic polyisocyanates such as are disclosed, for example, in DE-PS 2 404 310, column 3, line 39 to column 4, line 56.
• Organic polyisocyanates with exclusively aromatically bound isocyanate groups and an (average) NCO functionality of 2 to 2.3 are preferably used in the process according to the invention.
• the particularly preferred polyisocyanates include polyisocyanates or polyisocyanate mixtures of the diphenylmethane series which are liquid at room temperature, i.e.
• Component b1) is a chain extender of the type known per se, ie (i) alkanediols which may have ether groups and have a molecular weight of 62 to 400, (ii) aromatic diamines of molecular weight 108 to 400 or (iii) any mixtures of such chain extenders.
• Suitable chain extenders (i) are, for example, ethylene glycol, 1,2-dihydroxypropane, 1,3-dihydroxypropane, 1,4-dihydroxybutane, 1,6-dihydroxyhexane, 1,8-dihydroxyoctane, neopentylglycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, Tripropylene glycol, dibutylene glycol, tripropylene glycol or any mixtures of such diols.
• Suitable chain extenders (ii) are any aromatic diamines preferably having primary amino groups in the molecular weight range 108 to 400, i.e. Diamines which have exclusively aromatically bound, preferably primary, amino groups. Examples of such diamines are 1,4-diamino-benzene, 2,4-diaminotoluene, 2,4'- and / or 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diamino-diphenylmethane or 4 , 4'-Diaminodiphenyl-propane (2,2), or any mixture of such diamines.
• the preferred diamines to be used in the process according to the invention are those which have an alkyl substituent in at least one ortho position to the amino groups, in particular those which have at least one alkyl substituent ortho to the first amino group and in ortho position to the second amino group two alkyl substituents each with 1 to 4, preferably 1 to 3 carbon atoms, particularly preferably around those which in each case have at least one ortho position to the amino groups, an ethyl, n-propyl and / or isopropyl substituent and optionally in further ortho positions to the amino groups have methyl substituents.
• Examples of preferred or particularly preferred diamines are 2,4-diaminomesitylene, 1,3,5-triethyl-2,4-diaminobenzene, 1,3,5-triisopropyl-2,4-diaminobenzene, 1-methyl-3,5 -diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 4,6-dimethyl-2-ethyl-1,3-diaminobenzene, 3,5,3 ', 5' -Tetraethyl-4,4'-diaminodiphenylmethane, 3,5,3 ', 5'-tetraisopropyl-4,4'-diaminodiphenylmethane, 3,5-diethyl-3', 5'-diisopropyl-4,4'-diaminodiphenylmethane, 1,3-dimethyl-5-
• the diamines exemplified under (ii), in particular the diamines designated as preferred or particularly preferred, are used as the sole component b1).
• Component b2) is an organic polyhydroxyl compound from functionality and the hydroxyl group content calculable average molecular weight of 1800 to 12000, preferably 3000 to 7000 and an average hydroxyl functionality of 2 to 3, preferably 3. Mixtures of various polyhydroxyl compounds are often used as component b2), it also being conceivable that individual components of such mixtures have a molecular weight above 400 and below 1800 and / or a hydroxyl functionality above 3.
• Suitable polyhydroxyl compounds of the type mentioned are, in particular, the polyester and preferably polyether polyols known from polyurethane chemistry, as are mentioned, for example, in US Pat. No. 4,218,543, column 7, line 29 to column 8, line 55.
• the reaction partner for the polyisocyanate component a) is the "polyol component” b), which in turn is a solution of the chain extenders b1) in the higher molecular weight polyhydroxyl compounds b2).
• Component b1) is dissolved in an amount of 5 to 50% by weight, preferably 8 to 35% by weight, based on the amount of component b2), or combined with it to form a liquid mixture at room temperature .
• the preferred catalysts include the tin catalysts known per se, e.g. Tin (II) salts of carboxylic acids such as tin (II) acetate, tin (II) octoate, tin (II) ethylhexoate and tin (II) laurate and the dialkyl tin salts of carboxylic acids, e.g.
• Synergistic catalyst combinations of this type are e.g. described in German Offenlegungsschriften 24 34 185, 26 01 082 and 26 03 834.
• suitable catalysts to be used are tertiary amines of the type known per se, e.g.
• the preferred catalyst of this type is 1,4-diazabicyclo (2,2,2) octane.
• Further examples of catalysts to be used according to the invention and details of the mode of action of the catalysts are in the plastics manual, volume VII, edited by Vieweg and Höchtlen, Carl Hanser Verlag, Kunststoff 1966, e.g. described on pages 96 to 102.
• the catalysts are generally used in an amount of 0.001 to 10, preferably 0.05 to 1,% by weight, based on the amount of component b2), and preferably in this, together with component b1), when carrying out the process according to the invention. solved.
• Component d which is essential to the invention, is an ester group-containing reaction product of 3 to 15, preferably 5 to 10, moles of ricinoleic acid with 1 mole of a mono- or polyhydric alcohol having a molecular weight of 32 to 400, preferably 62 to 400, or a total of one mole of a mixture several such alcohols.
• the reaction products containing ester groups have an osmometrically determinable molecular weight of 900 to 4500, an acid number of less than 5, preferably less than 3 and a hydroxyl number of 12.5 to 125, preferably 20 to 75, and are generally oily liquids at 25 ° C. Viscosity from 200 to 3000 mPa.s represents.
• Any alcohols of the abovementioned molecular weight range ie any such alkanols or cycloalkanols, which may have ether groups, can be used to produce the release agents d) essential to the invention.
• Examples are methanol, ethanol, n-hexanol, n-dodecanol, n-octadecanol, the alkane diols exemplified under b1) (i) above, which may have ether groups, cyclohexanol, 1,4-dihydroxycyclohexane, glycerol or trimethylolpropane. Any mixtures of such alcohols can also be used.
• alkane diols of molecular weight range 62 to 400 of the type exemplified above under b1) (i) are optionally used in the preparation of the release agents.
• Ethylene glycol, 1,2- and 1,3-dihydroxypropane, 1,2-, 1,3-, 1,4- or 2,3-dihydroxybutane, neopentyl glycol, 1,4-bis-hydroxymethyl-cyclohexane, 1 are particularly preferred , 8-Dihydroxyoctan and very particularly preferably 1,6-dihydroxyhexane used as an alcohol component in the preparation of the release agents.
• the release agents d) essential to the invention are prepared from the starting materials mentioned by way of example by esterification reactions known per se, for example by heating the starting materials in the presence of catalytic amounts of a Lewis or Bronsted acid such as e.g. Sulfuric acid, p-toluenesulfonic acid, acidic ion exchangers, tin dichloride or titanium tetrabutylate at a pressure of approx. 1000 to 0.1 mbar at temperatures of up to 220 ° C., preferably up to 180 ° C. with simultaneous removal of the water formed in the condensation reaction.
• a Lewis or Bronsted acid such as e.g. Sulfuric acid, p-toluenesulfonic acid, acidic ion exchangers, tin dichloride or titanium tetrabutylate
• the release agents can also be produced by the azeotropic process in the presence of an organic solvent, e.g. Toluene as an entrain
• the release agents d) essential to the invention can be incorporated into both the polyisocyanate component a) and the polyol component b).
• the release agents of the polyisocyanate component a) are added at elevated temperatures of, for example, 30 to 100 ° C., so that the release agents react with part of the polyisocyanate to form urethane. Since the release agents containing hydroxyl groups react with part of the polyisocyanate component in the sense of an addition reaction anyway during the production of the molded articles and thus ultimately exist in the molded article in a chemically incorporated form, this last-mentioned variant amounts to the practically the same end result.
• the release agents d) essential to the invention are generally used in an amount of 0.3 to 30, preferably 1 to 10,% by weight, based on the entire reaction mixture.
• auxiliaries and additives which may also be used also include, for example, low-molecular, higher-functionality alcohols, such as, for example, Glycerin, trimethylolpropane or sorbitol, which are optionally used together with the chain extenders b1) in order to achieve any desired branching of the molecules.
• low-molecular, higher-functionality alcohols such as, for example, Glycerin, trimethylolpropane or sorbitol, which are optionally used together with the chain extenders b1) in order to achieve any desired branching of the molecules.
• the amount of polyisocyanate component a) is preferably such that there is an isocyanate index of 70 to 130, in particular 90 to 110, in the foamable mixture.
• the isocyanate index is the quotient of the number of isocyanate groups and the number of groups reactive towards isocyanates, multiplied by 100.
• the known reaction injection molding technique (RSG or RIM method) is used in particular.
• the amount of the mixture, which may be foamable is introduced into the mold in such a way that the molded body has an average total density of 0.8 to 1.4 g / cm 3 , preferably 0.9 to 1.2 g / cm.
• the moldings can be removed from the mold after a mold service life of 5 to 90, preferably 20 to 60 seconds.
• the temperature of the mold is 40 to 100 ° C, preferably 50 to 70 ° C.
• the method according to the invention permits For the first time, the problem-free series production of elastomeric, possibly microcellular shaped bodies of high density, without it being necessary to clean the molds used at short intervals.
• the excellent self-separating properties of the process products according to the invention are retained over at least 30 reaction cycles.
• release agents d) essential to the invention other release agents of the type known per se when carrying out the process according to the invention.
• other release agents of the type known per se when carrying out the process according to the invention.
• metal salts of long-chain carboxylic acids e.g. Zinc stearate.
• the process products according to the invention are particularly suitable for producing flexible automobile bumpers or flexible body elements.
• suitable variation of the starting materials in particular with a small proportion of diamond chain extenders of the type exemplified under b2), flexible shoe soles with good abrasion behavior and excellent mechanical strength can also be obtained, for example.
• reaction injection molding The formulations described in the following examples of use are processed using the reaction injection molding technique or "reaction injection molding” (RIM).
• Polyol mixture and polyisocyanate were fed to a high-pressure metering unit, optionally in a mixture with the mold release agent, and after intensive mixing in a positively controlled mixing head, they were pressed into a metal tool in the shortest possible time.
• the tool - a bowl shape made of tool steel - allows the production of a molded part of the following dimensions:
• the temperature of the raw materials is 35 ° C, the temperature of the tool 60 ° C.
• the mold life is set to 20 seconds and the cycle time to 60 seconds.
• the tool surface is treated with a commercially available release agent (Fluoricon 36-134, manufacturer Acmos 1) ). Eight molded parts can be removed from the mold, further demoulding will destroy the molded part.
• 25 molded parts can be easily removed from the mold, the build-up of a disturbing layer on the tool surface is not observed.
• Example 6 77.00 parts by weight of a polyether of OH number 28 according to Example 6, 23.00 parts by weight of the diamine mixture according to Example 6, 0.10 parts by weight of dibutyltin dilaurate 0.10 parts by weight of 1.4- Diazabicyclo- (2,2,2) octane and 7.50 parts by weight of an ester (DE-OS 21 21 670) from 1 mol of adipic acid, 6 mol of oleic acid and 3 mol of pentaerythritol (hydroxyl number approx. 50) become one Polyol component combined and processed with 53.00 parts by weight of the polyisocyanate from Example 6.
• the processing conditions are set as in Example 6.
• a polyether of OH number 28 according to Example 6 18.00 parts by weight of the diamine mixture according to Example 6, 0.10 parts by weight of dibutyltin dilaurate and 0.10 parts by weight of 1.4 Diazabicyclo- (2,2,2) octane are combined to a polyol component and with 47.00 parts by weight of a reaction product of tripropylene glycol and 4,4'-diphenylmethane diisocyanate (23% by weight NCO) according to the RSG method processed.
• the temperature of the raw materials is 35 ° C, the temperature of the tool 70 ° C.
• the mold life is set to 20 seconds and the cycle time to 60 seconds.
• the mold surface is treated with the mold release agent Chem Trend XMR 136 2 ) before the first molded part is manufactured. After only 3 demouldings, the tearing force became so high that further molded parts could only be removed from the tool under severe deformation.
• Example 9 The processing conditions are chosen as in Example 9. 30 demouldings could easily be carried out without deforming the molded parts.
• 76.10 parts by weight of a polyether of OH number 28 according to Example 6, 16.70 parts by weight of the diamine mixture according to Example 6, 0.10 parts by weight of dibutyltin dilaurate, 0.10 parts by weight of 1.4 Diazabicyclo- (2,2,2) octane and 7.00 parts by weight of the ester from Example 8 are combined into a polyol component and processed with 56.00 parts by weight of a reaction product of tripropylene glycol and 4,4'-diphenylmethane diisocyanate (23% by weight NCO) by the RSG process.
• Example 9 The processing conditions are chosen as in Example 9. Only 5 demouldings can be carried out, other molded parts are strongly deformed.
• the temperature of the raw materials is 35 ° C, the temperature of the tool 60 ° C.
• the mold life is set to 20 seconds and the cycle time to 60 seconds.
• the tool surface is treated with a commercially available release agent (Frekot (R) -X 5, manufacturer Frekote Inc. l )).
• More than 50 molded parts can be easily removed from the mold, the build-up of a disruptive layer on the tool surface is not observed.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Organic Chemistry (AREA)
• Polymers & Plastics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Emergency Medicine (AREA)
• Mechanical Engineering (AREA)
• Polyurethanes Or Polyureas (AREA)
• Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
• Injection Moulding Of Plastics Or The Like (AREA)
• Moulds For Moulding Plastics Or The Like (AREA)

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• 1984
  • 1984-10-03 DE DE19843436163 patent/DE3436163A1/de not_active Withdrawn
• 1985
  • 1985-09-16 AU AU47498/85A patent/AU571112B2/en not_active Ceased
  • 1985-09-19 US US06/777,656 patent/US4609682A/en not_active Expired - Fee Related
  • 1985-09-23 DE DE8585112040T patent/DE3563214D1/de not_active Expired
  • 1985-09-23 EP EP85112040A patent/EP0180749B1/fr not_active Expired
  • 1985-09-27 CA CA000491811A patent/CA1252945A/fr not_active Expired
  • 1985-10-02 JP JP60218184A patent/JPS6191216A/ja active Granted
  • 1985-10-02 ES ES547490A patent/ES8609392A1/es not_active Expired
  • 1985-10-02 BR BR8504862A patent/BR8504862A/pt not_active IP Right Cessation

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